Site-selective redox isomerizations of furanosides using a combined arylboronic acid/photoredox catalyst system,Chemical Science

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Site-selective redox isomerizations of furanosides using a combined arylboronic acid/photoredox catalyst system
Chemical Science ( IF 7.6 ) Pub Date : 2020/01/03 , DOI: 10.1039/c9sc05173b
Victoria Dimakos ₁ , Daniel Gorelik ₁ , Hsin Y Su ₁ , Graham E Garrett ₁ , Gregory Hughes ₂ , Hiromitsu Shibayama ₁ , Mark S Taylor ₁

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In the presence of an arylboronic acid and a hydrogen atom transfer mediator under photoredox conditions, furanoside derivatives undergo site-selective redox isomerizations to 2-keto-3-deoxyfuranosides. Experimental evidence and computational modeling suggest that the transformation takes place by abstraction of the hydrogen atom from the 2-position of the furanoside-derived arylboronic ester, followed by C3–O bond cleavage via spin-center shift. This mechanism is reminiscent of the currently accepted pathway for the formation of 3′-ketodeoxynucleotides by ribonucleotide reductase enzymes.

中文翻译：

使用组合芳基硼酸/光氧化还原催化剂体系进行呋喃糖苷的位点选择性氧化还原异构化

在光氧化还原条件下，芳基硼酸和氢原子转移介体存在下，呋喃糖苷衍生物会发生位点选择性氧化还原异构化，生成 2-酮-3-脱氧呋喃糖苷。实验证据和计算模型表明，该转化是通过从呋喃糖苷衍生的芳基硼酸酯的 2-位上夺取氢原子，然后通过自旋中心位移发生 C3-O 键断裂而发生的。这种机制让人想起目前公认的通过核糖核苷酸还原酶形成 3'-酮脱氧核苷酸的途径。

更新日期：2020-02-13

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